EP2817370B1 - Fluorinated acrylate block copolymers with low dynamic surface tension - Google Patents

Fluorinated acrylate block copolymers with low dynamic surface tension Download PDF

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EP2817370B1
EP2817370B1 EP13706244.4A EP13706244A EP2817370B1 EP 2817370 B1 EP2817370 B1 EP 2817370B1 EP 13706244 A EP13706244 A EP 13706244A EP 2817370 B1 EP2817370 B1 EP 2817370B1
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alkyl
block
block copolymer
meth
use according
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German (de)
French (fr)
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EP2817370A1 (en
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Mary Thomson
Ralf Knischka
Clemens Auschra
Lothar Engelbrecht
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

  • the present invention relates to a composition which comprises a block copolymer having fluorinated monomer units and to the use of said block copolymer as substrate wetting, anti-cratering and/or leveling agent for coating, ink and/or adhesive compositions.
  • US 2004/0254268 A1 discloses a composition comprising a polymer processing aid and at least one coupling agent having controlled polymer architecture. Said composition can be used for preparing building materials and automotive components.
  • WO 03/027159 A2 discloses a composition comprising a block copolymer comprised of: (a) a first block comprising residues of a first radically polymerizable low surface tension (meth) acrylate monomer; and (b) a second block comprising residues of a second radically polymerizable ethylenically unsaturated monomer that is free of hydroxyl groups and amine groups.
  • WO 03/033603 A1 discloses the use of a polymer as a levelling agent or anti-cratering agent, said polymer comprising at least one fluorinated unit. WO 03/033603 A1 does not address dynamic surface tension properties.
  • the block B may consist of monomer units derived from the fluorinated (meth)acrylic ester compound of formula (I) or from the fluorinated alpha-olefin of formula (II).
  • the block B may contain two or more different monomer units.
  • block copolymer contains two or more blocks of type "B", they may differ in block length (i.e. different number of monomer units), but preferably have the same arrangement or sequence of monomer units.
  • the block B of the block copolymer has an average number of monomer units which are derived from the fluorinated (meth)acrylic ester compound of formula (I) and/or from the fluorinated alpha-olefin of formula (II) of at least 0.25, more preferably at least 0.5, or at least 1.
  • the block A may consist of monomer units derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, or a vinyl aromatic compound.
  • the block A may contain two or more different monomer units.
  • block copolymer contains two or more blocks of type "A", they may differ in block length (i.e. different number of monomer units), but preferably have the same arrangement or sequence of monomer units.
  • the block A of the block copolymer has an average number of monomer units which are derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, or a vinyl aromatic compound, of at least 5, more preferably at least 10, even more preferably at least 15.
  • the block A of the block copolymer has an average number of monomer units which are derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, or a vinyl aromatic compound, of from 5 to 1000, more preferably from 10 to 500, even more preferably from 15 to 300.
  • the block copolymer has a number average molecular weight Mn of from 1000 to 100,000 g/mol, more preferably from 2,000 to 50,000 g/mol, even more preferably 3,000 to 25,000 g/mol.
  • Mn number average molecular weight
  • Other appropriate Mn ranges that can be used in the present invention are e.g. from 3,000 to 100,000 g/mol, or from 4,000 to 100,000 g/mol, or from 6,000 to 50,000 g/mol.
  • the block copolymer comprises the monomer units derived from the fluorinated (meth)acrylic ester of formula (I) and/or from the fluorinated alpha-olefin of formula (II) in an amount of from 0.1 wt% to 70 wt%, more preferably from 0.5 wt% to 50 wt%, even more preferably from 1 wt% to 25 wt%.
  • the block copolymer has a fluorine content of from 0.05 wt% to 35 wt%, more preferably from 0.25 wt% to 25 wt%, even more preferably from 0.5wt% to 17 wt%.
  • the block copolymer has a polydispersity index PDI (i.e. Mw/Mn) of less than 1.90, more preferably of less than 1.60, even more preferably of less than 1.40, or even less than 1.30.
  • PDI polydispersity index
  • the polydispersity index PDI may depend on the number of blocks being present and their arrangement in the block copolymer. If the block copolymer is linear with one block of A and one block of B, PDI may preferably be less than 1.40, more preferably less than 1.30. If the block copolymer is linear with one block of A and two blocks of B, or alternatively with one block of B and two blocks of A, PDI may preferably be less than 1.60, more preferably less than 1.50.
  • the block copolymer is preferably obtained by a controlled free radical polymerization (sometimes also referred to as "controlled radical polymerization”). Methods of "controlled free radical polymerization” are generally known to the skilled person.
  • the controlled free radical polymerization is selected from nitroxide-mediated controlled polymerization (NMP), atom transfer radical polymerization (ATRP), or from reversible addition-fragmentation chain transfer polymerization (RAFT).
  • NMP nitroxide-mediated controlled polymerization
  • ATRP atom transfer radical polymerization
  • RAFT reversible addition-fragmentation chain transfer polymerization
  • reversible addition-fragmentation chain transfer polymerisation RAFT using chain transfer agents which react by reversible addition- fragmentation chain transfer is described, for example, in WO-A-98/01478 , WO-A-99/05099 , WO-A-99/31144 , and WO 2009/103613 .
  • the controlled radical polymerization is selected from nitroxide-mediated controlled polymerization (NMP) and atom transfer radical polymerization (ATRP), even more preferably from NMP.
  • NMP nitroxide-mediated controlled polymerization
  • ATRP atom transfer radical polymerization
  • the controlled radical polymerization is a nitroxide-mediated controlled polymerization, which preferably uses a polymerization regulator system based on polymerization regulator compounds being preferably selected from one of the following formulas (IV), (V) and (VI) or based on the corresponding stable free nitroxyl radicals in conjunction with a radical source: wherein
  • controlled free radical polymerization may involve using an initiator fragment IN for initiating the radical polymerization.
  • the initiator fragment can be released from a polymerization regulator compound IN-E, e.g. from one of those described above.
  • radical X represents the initiator fragment IN
  • the nitroxide radical would represent the group E.
  • a block can also be defined as a region of the polymer chain that is richer in fluorinated monomer than another block.
  • the block copolymer of the present invention may contain only one block A, or may contain two or more blocks of A.
  • the blocks may have the same number of monomer units or may differ in block length (i.e. different number of monomer units).
  • the amount of the block copolymer, relative to the total composition is from 0.05 wt% to 15 wt%, more preferably from 0.075 wt% to 10 wt% and most preferred from 0.1 wt% to 5 wt%.
  • compositions include a solvent-based coating composition, a water-based coating composition, a high solids coating composition, a powder coating composition, a solvent-borne ink composition, a water-borne ink composition, a UV-curable ink composition, or a UV-curable coating composition, or combinations thereof.
  • reducing dynamic surface tension means that dynamic surface tension is lower if compared to a random but otherwise identical copolymer.
  • Mn and PDI are measured by gel permeation chromatography (GPC) with polystyrene standards.
  • the eluent is THF.
  • the polymer is characterized by GPC (THF and with PS-Standards) and 1 H-NMR (in CDCl 3 ).
  • Product C (g of nBA)
  • D (g of TFOA)
  • E (g NOR1) Yield (%) Mn a (g/mol) PDI a wt.
  • the polymer is characterized by GPC (THF and with PS-Standards) and 1 H-NMR (in CDCl 3 ).
  • Product B (g of nBA)
  • A (g of TFOA)
  • C (g of tBpOEH)
  • Mn a (g/mol)
  • PDI a wt.% TFOA b wt% F in polymer b
  • GK3365-133 88.54 5.00 6.46 2065 1.56 5.35 2.95
  • GK3365-134 83.54 10.00 6.46 2072 1.56 10.69 5.90
  • nBA n-Butyl Acrylate
  • NOR 2 NOR 2
  • H g of di-functional poly nBA (see table) and I g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 8 hours at 128°C. Residual monomer is distilled off at 105°C and 20 mbar.
  • the polymer is characterized by GPC (THF and with PS-Standards; note: the refractive index of TFOA is negative) and 1 H-NMR (in CDCl 3 ).
  • Product A-block Poly-nBA H (g of A block ) I (g TFOA ) Yield (%) Mn a (g/mol ) PDI a wt.
  • the polymer is characterized by GPC (THF and with PS-Standards) and 1 H-NMR (in CDCl 3 ).
  • Product C (g of nBA)
  • D (g of NFHA)
  • E (g NOR1) Yield (%) Mn a (g/mol)
  • PDI a wt.% NFHA b wt% F in polymer b
  • GK3479-202 50.86 9.70 3.00 50.79 2786 1.25 21.01 11.14
  • GK3479-203 54.07 6.48 3.00 51.94 2896 1.19 17.39 9.22 GK3479-204 57.35 3.20 3.00 49.08 2847 1.23 12.36 6.55
  • GK3479-205 50.86 9.70 0.95 49.75 8146 1.18 19.62 10.40
  • GK3479-206 54.07 6.48 0.95 51.24 8189 1.19 18.96 10.05 GK3479-207 57.35 3.20 0.95 52.87 8552
  • the polymer is characterized by GPC (THF and with PS-Standards) and 1 H-NMR (in CDCl 3 ).
  • Product B g of nBA
  • A g of NFHA
  • PDI a wt.% NFHA b wt% F in polymer b
  • Static surface tension is measured using an OCA 20 (Dataphysics) at concentrations from 1 - 10 w% in xylene using the hanging-drop method.
  • Example type conc (w%) 10 1 comparative Xylol (blank) 28,62 28,62 GK3479/022 12,6 28,45 28,98 GK3479/021 17,7 27,83 29,03 GK3479/020 21,5 27,1 28,93 inventive GK3479/047 3,7 28,22 28,98 GK3479/042 10,2 20,76 25,93 GK3494/026 14,9 18,55 21,29 GK3494/027 24,9 18,34 19,62
  • Dynamic surface tension is measured using a bubble pressure tensiometer (Sita) at concentrations of 0.25 % 0,5 w% in the A component of a solventbased 2K-PU. Bubble life times are measured from 80 msec up to 10 sec.
  • a component 2K PU Table 2.1 2K-PU Component A Raw material Identity Weight in g. 0.25wt% Additive 0.5wt% Additive Macrynal SM510/60LG Acrylic resin solution 89.0 Butyl acetate Solvent 11,0 Efka® 2018N 8.0 Formulation 108.0 7,38 7,36 Additive 0.025 0.05 Sample size 7.405 7.41
  • Efka 2018N is a commercially available defoamer.
  • Dynamic surface tension is measured using a bubble pressure tensiometer (Sita) at concentrations of 0.1 % 1.0 w% in the A component of a solventbased 2K-PU. Bubble life times are measured from 80 msec up to 10 sec. In the following test series the commercial leveling additive EFKA 3600N is used a reference.
  • a component 2K PU Table 2.1 2K-PU Component A Raw material Identity Weight in g. 0.25wt% Additive Macrynal SM510/60LG Acrylic resin solution 89.0 Butyl acetate Solvent 11,0 Formulation 100.0 19,95 Additive 0.05 Sample size 20,00

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Description

  • The present invention relates to a composition which comprises a block copolymer having fluorinated monomer units and to the use of said block copolymer as substrate wetting, anti-cratering and/or leveling agent for coating, ink and/or adhesive compositions.
  • Smooth and crater free surfaces are important for almost all coating, ink and adhesive applications; they provide not only a visually appealing film but serve also as a protective barrier for the substrate as well as homogenous bondstrength throughout the film.
  • When e.g. the coating is not homogenous and some parts of the surface are only thinly, or not all, coated it leads to poor protection of the substrate. As a result, substrate wetting, anti cratering and leveling agents are added to all sorts of coatings. These difficulties in application of coating resin, particularly in liquid systems, occur particularly when the surface tension of the liquid system is high and the surface tension of the substrate, or contaminants on the substrate, is much lower. The addition of substrate wetting and anti cratering additives reduces both the dynamic and static surface tension of the liquid coating, leading to smoother film formation.
  • As long as the viscosity of the coating formulation is low, sufficient substrate wetting and leveling can be achieved with commercially available additives. Large problems can be observed in the cases of high solids coatings, powdered coatings and high speed coating processes. There is a strong demand for substrate wetting and anti-cratering additives with a very low dynamic surface tension, which can provide smooth and uniform films in these highly demanding applications.
  • The same reasoning applies also for inks and adhesives.
  • Long chain perfluoro chemicals, typically with perfluorinated chains of length C8 and longer, are used as anti-cratering and leveling agents for coating compositions but are known to form very environmentally persistent degradation products, including perfluoro-octanoic acid (PFOA). Thus, there is a need for alternatives which do not form such environmentally persistent degradation products. However, any improvement in degradation properties should not be achieved at the expense of properties which are relevant for leveling agents such as low dynamic surface tension. In general, the effect on dynamic surface tension reduction is believed to decrease with the order of the perfluorinated unit.
  • WO 2005/059048 describes coating compositions containing leveling agents prepared by nitroxide mediated polymerization. Monomer units may be substituted by fluoro or perfluoro.
  • WO 2009/103613 describes the use of short perfluorinated chains in copolymers prepared by nitroxide mediated polymerization for the use of leveling agents.
  • WO 2007/078819 A2 describes method of preparing a block co-polymer comprising a first block attached to a second block, the method comprising the steps of (a) preparing the first block by polymerizing a first monomer in the presence of a nitroxide; (b) preparing the second block by polymerizing a second monomer in the presence of the nitroxide; in which the first monomer and the second monomer each comprise an acrylic monomer, a methacrylic monomer, or a mixture thereof; and either the first monomer or the second monomer comprises a low surface energy monomer, or both the first monomer and the second monomer each comprise a low surface energy monomer. WO 2007/078819 A2 does not address dynamic surface tension properties.
  • US 2004/0254268 A1 discloses a composition comprising a polymer processing aid and at least one coupling agent having controlled polymer architecture. Said composition can be used for preparing building materials and automotive components.
  • WO 03/027159 A2 discloses a composition comprising a block copolymer comprised of: (a) a first block comprising residues of a first radically polymerizable low surface tension (meth) acrylate monomer; and (b) a second block comprising residues of a second radically polymerizable ethylenically unsaturated monomer that is free of hydroxyl groups and amine groups.
  • WO 03/033603 A1 discloses the use of a polymer as a levelling agent or anti-cratering agent, said polymer comprising at least one fluorinated unit. WO 03/033603 A1 does not address dynamic surface tension properties.
  • It is an object of the present invention to provide a polymeric leveling and anti-cratering agent which does not form environmentally very persistent degradation products such as perfluoro-octanoic acid but still enables manufacturing of coating, ink or adhesive compositions having very low dynamic surface tension.
  • The object is solved by using a block copolymer which comprises at least a block A and a block B, wherein
    • the block A comprises monomer units derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, a vinyl aromatic compound, or any mixture thereof,
    • the block B comprises monomer units derived from a compound selected
      • from a fluorinated (meth)acrylic ester having the following formula (I):

                H2C=CR1(C(O)ORF-1)     (I)

        wherein
        • R1 is H or methyl; and
        • RF-1 is an organic residue containing a perfluorinated C4-6 alkyl
        • group, i.e. -(CF2)3-5-CF3,
      • a fluorinated alpha-olefin having the following formula (II):

                H2C=CH(RF-2)     (II)

        wherein RF-2 is an organic residue containing a perfluorinated C4-6 alkyl group, i.e. -(CF2)3-5-CF3
      • or any mixture thereof,
      as a dynamic surface tension reducing additive in a coating composition, ink composition or adhesive composition.
  • A perfluorinated C4-6 alkyl group is represented by the formula -(CF2)3-5-CF3.
  • Preferably, RF-1 and RF-2, which can be the same or different, have the following formula (III):

            -(R2)x-(CF2)3-5-CF3     (III)

    wherein x is 0 or 1; and R2 is a divalent non-fluorinated C1-4 alkylene group, which can be substituted or unsubstituted.
  • In a preferred embodiment, R2 in formula (III) is -(CH2)1-4-; such as -CH2-; -CH2-CH2-; -CH2-CH2-CH2-; or -CH2-CH2-CH2-CH2-.
  • In a preferred embodiment, the fluorinated (meth)acrylic ester compound of formula (I) is selected from 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoroctyl acrylate, 3,3,4,4,5,5,6,6,6-nonafluorhexyl-acrylate, or mixtures thereof.
  • Preferred fluorinated alpha-olefins of formula (II) include e.g. 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, or any mixture thereof.
  • The block B may consist of monomer units derived from the fluorinated (meth)acrylic ester compound of formula (I) or from the fluorinated alpha-olefin of formula (II).
  • Alternatively, the block B may contain two or more different monomer units.
  • If the block copolymer contains two or more blocks of type "B", they may differ in block length (i.e. different number of monomer units), but preferably have the same arrangement or sequence of monomer units.
  • Preferably, the block B of the block copolymer has an average number of monomer units which are derived from the fluorinated (meth)acrylic ester compound of formula (I) and/or from the fluorinated alpha-olefin of formula (II) of at least 0.25, more preferably at least 0.5, or at least 1.
  • If the average number of monomer units of a specific block is below 1, this means that, statistically, not every polymer chain contains monomer units of said block. However, when using the block copolymer of the present invention, a reduced dynamic surface tension is still obtained at such low amount of fluorinated monomer units.
  • In a preferred embodiment, the block B of the block copolymer has an average number of monomer units which are derived from the fluorinated (meth)acrylic ester compound of formula (I) and/or from the fluorinated alpha-olefin of formula (II) of from 0.25 to 40, more preferably 0.5 to 30, even more preferably 1 to 20.
  • Preferably, block A comprises monomer units derived from a compound selected from C1-18 (meth)acrylates, more preferably C1-10 (meth)acrylates, especially methyl(meth)acrylate (MMA), ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isodecyl(meth)acrylate, hydroxyl-functional (meth)acrylates like 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, acid functional (meth)acrylic monomers like acrylic acid or methacrylic acid, sulphonic acid containing monomers like 2-acrylamido-2-methylpropane sulfonic acid (AMPS), aminofunctional (meth)acrylates like dimethylaminoethylmethacrylate (DMAEMA), epoxy functional (meth)acrylates like glycidylmethacrylate (GMA), (meth)acrylates containing siloxane groups, vinyl aromatic compounds such as styrene, or any mixture thereof.
  • The block A may consist of monomer units derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, or a vinyl aromatic compound.
  • Alternatively, the block A may contain two or more different monomer units.
  • If the block copolymer contains two or more blocks of type "A", they may differ in block length (i.e. different number of monomer units), but preferably have the same arrangement or sequence of monomer units.
  • Preferably, the block A of the block copolymer has an average number of monomer units which are derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, or a vinyl aromatic compound, of at least 5, more preferably at least 10, even more preferably at least 15. In a preferred embodiment, the block A of the block copolymer has an average number of monomer units which are derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, or a vinyl aromatic compound, of from 5 to 1000, more preferably from 10 to 500, even more preferably from 15 to 300.
  • Preferably, the block copolymer has a number average molecular weight Mn of from 1000 to 100,000 g/mol, more preferably from 2,000 to 50,000 g/mol, even more preferably 3,000 to 25,000 g/mol. Other appropriate Mn ranges that can be used in the present invention are e.g. from 3,000 to 100,000 g/mol, or from 4,000 to 100,000 g/mol, or from 6,000 to 50,000 g/mol.
  • Preferably, the block copolymer comprises the monomer units derived from the fluorinated (meth)acrylic ester of formula (I) and/or from the fluorinated alpha-olefin of formula (II) in an amount of from 0.1 wt% to 70 wt%, more preferably from 0.5 wt% to 50 wt%, even more preferably from 1 wt% to 25 wt%.
  • Preferably, the block copolymer has a fluorine content of from 0.05 wt% to 35 wt%, more preferably from 0.25 wt% to 25 wt%, even more preferably from 0.5wt% to 17 wt%.
  • Preferably, the block copolymer has a polydispersity index PDI (i.e. Mw/Mn) of less than 1.90, more preferably of less than 1.60, even more preferably of less than 1.40, or even less than 1.30.
  • The polydispersity index PDI may depend on the number of blocks being present and their arrangement in the block copolymer. If the block copolymer is linear with one block of A and one block of B, PDI may preferably be less than 1.40, more preferably less than 1.30. If the block copolymer is linear with one block of A and two blocks of B, or alternatively with one block of B and two blocks of A, PDI may preferably be less than 1.60, more preferably less than 1.50.
  • The block copolymer is preferably obtained by a controlled free radical polymerization (sometimes also referred to as "controlled radical polymerization"). Methods of "controlled free radical polymerization" are generally known to the skilled person.
  • In a preferred embodiment, the controlled free radical polymerization is selected from nitroxide-mediated controlled polymerization (NMP), atom transfer radical polymerization (ATRP), or from reversible addition-fragmentation chain transfer polymerization (RAFT). These polymerization methods and variants thereof are generally known to the skilled person.
  • The reversible addition-fragmentation chain transfer polymerisation RAFT using chain transfer agents which react by reversible addition- fragmentation chain transfer is described, for example, in WO-A-98/01478 , WO-A-99/05099 , WO-A-99/31144 , and WO 2009/103613 .
  • RAFT describes a method of polymer synthesis by radical polymerization in the presence of a free radical source and using chain transfer agents which react by reversible addition- fragmentation chain transfer. The chain transfer agent is, for example,
    • 2-phenylprop-2-yl dithiobenzoate (Ph-C(CH3,CH3)-S-C(S)-Ph) or benzyl dithioacetate Ph-CH2-S-C(S)-CH3 as described in WO 98/01478 ,
    • carbamates such as benzyl 1-pyrrolecarbodithioate, as described in WO99/31144 ;
    • alkylxanthates such as ethyl α(O-ethylxanthyl propionate), as described in WO 98/58974 .
  • WO 96/30421 discloses a controlled polymerisation process of ethylenically unsaturated polymers, such as styrene or (meth)acrylates, by employing the Atomic Transfer Radical Polymerisation (ATRP) method. This method produces defined oligomeric homopolymers and copolymers, including block copolymers. Initiators are employed, which generate radical atoms, such as •Cl, in the presence of a redox system of transition metals of different oxidation states, e.g. Cu(I) and Cu(II), providing "living" or controlled radical polymerisation.
  • Details about nitroxide-mediated controlled polymerization are described e.g. in WO 2005/059048 and WO 2009/103613 . The initiator compounds described therein can be used in the present invention as well.
  • More preferably, the controlled radical polymerization is selected from nitroxide-mediated controlled polymerization (NMP) and atom transfer radical polymerization (ATRP), even more preferably from NMP.
  • In a preferred embodiment, the controlled radical polymerization is a nitroxide-mediated controlled polymerization, which preferably uses a polymerization regulator system based on polymerization regulator compounds being preferably selected from one of the following formulas (IV), (V) and (VI) or based on the corresponding stable free nitroxyl radicals in conjunction with a radical source:
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
     wherein
    • - R is hydrogen, C1-18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
    • - R101 is C1-12alkyl, C5-7cycloalkyl, C7-8aralkyl, C2-18alkanoyl, C3-5alkenoyl or benzoyl;
    • - R102 is C1-18alkyl, C5-7cycloalkyl, C2-8alkenyl, which can be unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(OH)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl;
    • - G6 is hydrogen,
    • - G5 is hydrogen or C1-4alkyl,
    • - G1 and G3 are methyl,
    • - G2 and G4 are ethyl or propyl, or G1 and G2 are methyl and G3 and G4 are ethyl or propyl; and
    • - X is selected from -CH2-phenyl, CH3CH-phenyl, (CH3)2C-phenyl, (C5-6cycloalkyl)2CCN, (CH3)2CCN,
      Figure imgb0004
       -CH2CH=CH2, CH3CH-CH=CH2 , (C1-4alkyl)CR20-C(O)-phenyl, (C1-4)alkyl-CR20-C(O)-(C1-4)alkoxy, (C1-4)alkyl-CR20-C(O)-(C1-4)alkyl, (C 1-4)alkyl-CR20-C(O)-N-di(C1-4)alkyl, (C1-4)alkyl-CR20-C(O)-NH(C1-4)alkyl, (C1-4)alkyl-CR20-C(O)-NH2, wherein R20 is hydrogen or (C1-4)alkyl; and wherein any of the alkyl groups can be unsubstituted or substituted, e.g. by one or more functional groups such as hydroxyl, amino, carboxylic acid, halide, cyano, and/or carbonyl.
  • The above polymerization regulator compounds as well as their corresponding stable free nitroxl radicals and their preparation are described in GB 2 335 190 and GB 2 361 235 .
  • As known to the skilled person, controlled free radical polymerization may involve using an initiator fragment IN for initiating the radical polymerization. The initiator fragment can be released from a polymerization regulator compound IN-E, e.g. from one of those described above. In formulas (IV) to (VI), radical X represents the initiator fragment IN, whereas the nitroxide radical would represent the group E.
  • The block copolymer can be a diblock copolymer, a triblock copolymer, or multiblock copolymer.
  • The block copolymer can be linear, or branched (such as star-shaped, comb-shaped, etc.).
  • In the present invention, the term "block copolymer" also includes a gradient and/or tapered block copolymer. This type of structured copolymer is also generally known to the skilled person. In a gradient or tapered block copolymer, there is a gradient compositional transition between blocks A and B.
  • In a preferred embodiment, a block can also be defined as a region of the polymer chain that is richer in fluorinated monomer than another block.
  • In the block copolymer of the present invention, two neighbouring blocks can be directly linked to each other. Alternatively, two neighbouring blocks can be linked to each other via a linking group LG, e.g. -A-LG-B- ; -B-LG-B- ; -A-LG-A-
  • The linking group LG can be any divalent group which may form a covalent bond to blocks A and B. Appropriate linking groups are known to the skilled person.
  • In a preferred embodiment, the linking group LG has the following formula (VII):

            -IN1'-Y'-IN2'-     (VII)

    wherein the IN1' and IN2' groups, which can be the same or different, are derived from the initiator fragments IN1 and IN2 of the controlled free radical polymerization, and Y' is a divalent group covalently linked to the IN1' and IN2' groups or represents a covalent bond (e.g. σ-bond or π-bond) between the IN1' and IN2' groups.
  • Preferably, the initiator fragments IN1 and IN2 are the same and, consequently, the IN1' and IN2' groups are the same as well.
  • The divalent group Y' can be derived from a compound Y having at least two functional groups which may react with the initiator fragments IN1 and IN2. Appropriate compounds having at least two functional groups are e.g. diisocyanate compounds (such as toluene diisocyanate), aliphatic polyisocyanates or isocyanurate compounds.
  • The linking group LG of formula (VII) can be obtained by using, in the controlled free radical polymerization, an initiator fragment IN having at least one functional group, such as hydroxyl, amino, carboxylic acid, halide, cyano, and/or carbonyl. After having initiated controlled free radical polymerization, the initiator fragment IN is covalently bonded to one end of the polymer chain. In the presence of a compound Y having two functional groups, a chemical reaction between said compound Y and two IN groups of two different polymer chains may take place, thereby bonding these polymer chains to each other via a linking group of formula (VII).
  • The block copolymer of the present invention may contain only one block A, or may contain two or more blocks of A. The blocks may have the same number of monomer units or may differ in block length (i.e. different number of monomer units).
  • The block copolymer of the present invention may contain only one block B, or may contain two or more blocks of B. The blocks may have the same number of monomer units or may differ in block length (i.e. different number of monomer units).
  • If the block copolymer contains at least two blocks of A and at least two blocks of B, the block copolymer may comprise the following structural element:

            -B-A-LG-A-B- or -A-B-LG-B-A-

    wherein LG is the linking group described above, which is preferably of formula (VII).
  • Preferably, the amount of the block copolymer, relative to the total composition, is from 0.05 wt% to 15 wt%, more preferably from 0.075 wt% to 10 wt% and most preferred from 0.1 wt% to 5 wt%.
  • The composition for which the block copolymer described above is used as a dynamic surface tension reducing additive is a coating composition, an ink composition or an adhesive composition.
  • Exemplary compositions include a solvent-based coating composition, a water-based coating composition, a high solids coating composition, a powder coating composition, a solvent-borne ink composition, a water-borne ink composition, a UV-curable ink composition, or a UV-curable coating composition, or combinations thereof.
  • As indicated above, the present invention is directed to the use of the block copolymer described above for reducing dynamic surface tension in a coating composition, ink composition or adhesive composition, such as high solids coating compositions and powder coating compositions, ink compositions such as solvent-borne inks, water-borne inks, UV inks, UV coatings.
  • Preferably, the term "reducing dynamic surface tension" means that dynamic surface tension is lower if compared to a random but otherwise identical copolymer.
    • Examples I. Measuring methods
  • If not indicated otherwise, parameters defined in the present application are measured by the measuring methods described below:
    • Number average molecular weight Mn, polydispersity index PDI
  • Mn and PDI are measured by gel permeation chromatography (GPC) with polystyrene standards. The eluent is THF.
    • Amount of F (in wt%) and amount of fluorine-containing monomer units (in wt%) in the block copolymer
  • Determined by 1H NMR, 400 MHz.
    • II. Preparation Examples Inventive Example 1 Synthesis of a linear A-B Block-copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA) Synthesis of A block
  • Figure imgb0005
  • In a 5000 mL glass reactor with overhead mechanical stirrer, condenser, metering pumps, computerized temperature control and data acquisition, the following A-blocks are synthesized.
    • GK3023-360 (10 units nBA)
  • 1816.70 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol), 150.00 g of the initiator compound NOR 1 (317.48 g/mol) and 271.38 g of ethyl acetate (EtAc, Mw 88.11 g/mol) are mixed together, purged with N2 and reacted for 3 h at 120°C. Residual monomer and ethyl acetate is distilled off at 105°C and 20 mbar.
    Yield: 33.3%; GPC (THF, PS-Standard, Mn = 1706 g/mol, PDI = 1.26, liquid)
    • GK3023-264 (20 units)
  • 1211.13 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 60.00 g of the initiator compound NOR 1 (317.48 g/mol) are mixed together, purged with N2 and reacted for 3.5 h at 115°C. Residual monomer is distilled off at 105°C and 20 mbar.
    Yield: 42.83%; GPC (THF, PS-Standard, Mn = 2435 g/mol, PDI = 1.36, viscous liquid)
    • GK3023-335 (35 units)
  • 1383.92 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol), 40.00 g of the initiator compound NOR 1 (317.48 g/mol) and 206.70 g of ethyl acetate (EtAc, Mw 88.11 g/mol) are mixed together, purged with N2 and reacted for 3 h at 120°C. Residual monomer and ethyl acetate is distilled off at 105°C and 20 mbar.
    Yield: 38.3%; GPC (THF, PS-Standard, Mn = 3649 g/mol, PDI = 1.44, viscous liquid)
    • GK3023-387 (75 units)
  • 1211.13 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 60.00 g of NOR 1 (317.48 g/mol) are mixed together, purged with N2 and reacted for 1.5 h at 115°C. A feed of 2422.26 g of nBA is fed to the reactor over 3 hours. At 125°C, the reaction continues for a further 4.5 h. Residual monomer is distilled off at 105°C and 20 mbar.
    Yield: 50.36%; GPC (THF, PS-Standard, Mn = 9650 g/mol, PDI = 1.21, viscous liquid)
    • Synthesis of B block
  • Figure imgb0006
  • In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, A g of Poly-nBA (see table) and B g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 8 hours at 128°C. Residual monomer is distilled off at 105°C and 20 mbar. The polymer is characterized by GPC (THF and with PS-Standards; note: the refractive index of TFOA is negative) and 1H-NMR (in CDCl3).
    Product A-block Poly-nBA A (g of A block) B (g TFOA) Yield (%) Mn a (g/mol) PDI a wt. % TFOA b wt% F in polymer b Description (units of nBA: units of TFOA)b
    GK3479-039 GK3023-360 10.00 13.94 82.59 2029 1.29 50.90 30.03 10:3.96
    GK3479-040 GK3023-360 15.00 12.54 88.56 2035 1.23 40.40 23.87 10:2.59
    GK3479-041 GK3023-360 20.00 5.58 89.12 1771 1.22 19.07 11.25 10:0.90
    GK3479-076 GK3023-360 27.00 3.00 87.93 2055 1.21 7.51 4.43 10:0.31
    GK3479-077 GK3023-360 27.90 2.10 88.40 2016 1.22 5.91 3.49 10:0.24
    GK3479-044 GK3023-264 20.00 13.94 95.01 3510 1.20 36.93 21.79 20:4.03
    GK3479-046 GK3023-264 20.00 8.36 92.01 3121 1.22 24.97 14.73 20:2.29
    GK3494-071 GK3023-264 30.00 4.18 92.44 3377 1.24 10.30 6.07 20:0.79
    GK3494-014 GK3023-264 30.00 20.91 94.96 4331 1.22 37.22 21.96 20:4.08
    GK3479-080 GK3023-264 45.00 5.00 93.31 2949 1.26 6.26 3.70 20:0.46
    GK3479-081 GK3023-264 46.50 3.50 93.57 3012 1.26 4.97 2.93 20:0.36
    GK3479-043 GK3023-335 30.00 7.84 94.09 4476 1.17 17.36 10.24 35:2.41
    GK3494-028 GK3023-335 30.00 13.07 91.04 5068 1.16 28.26 16.67 35:4.53
    GK3479-070 GK3023-335 30.00 2.61 96.33 5218 1.19 6.29 3.71 35:0.77
    GK3479-079 GK3023-335 27.00 3.00 96.90 4869 1.20 6.21 3.66 35:0.76
    GK3494-026 GK3023-387 50.00 10.59 94.47 8638 1.16 14.89 8.78 75:4.15
    GK3494-027 GK3023-387 50.00 20.91 91.77 9119 1.18 24.86 14.67 75:7.85
    GK3479-042 GK3023-387 50.00 6.27 98.86 8223 1.19 10.22 6.03 75:2.70
    GK3479-047 GK3023-387 50.00 2.09 98.93 8012 1.19 3.65 2.16 75:0.90
    GK3479-078 GK3023-387 45.00 5.00 97.24 9907 1.23 7.81 4.61 75:2.01
    GK3479-48c GK3023-387 40.00 14.65 83.99 7803 1.19 5.19 3.06 75:1.30
    GK3479-082 GK3023-387 46.50 3.50 98.11 9476 1.22 5.80 3.42 75:1.46
    a by GPC with polystyrene standards
    b by H1 NMR
    c Polymerization at 115°C for 2 hours.
    • Comparative Example 2 Synthesis of a linear, low polydispersity, random copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA) GK3479-027
  • Figure imgb0007
  • In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, C 65.70 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol), D 3.70 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol) and E 2.50 g of NOR 1 (317.48 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 3-4 hours at 125°C. Residual monomer is distilled off at 95°C and 10 mbar. The polymer is characterized by GPC (THF and with PS-Standards) and 1H-NMR (in CDCl3).
    Product C (g of nBA) D (g of TFOA) E (g NOR1) Yield (%) Mn a (g/mol) PDI a wt. % TFOA b wt% F in polymer b
    GK3479-027 65.70 3.70 2.50 60.14 3724 1.20 8.02 4.73
    GK3479-026 62.00 7.40 2.50 61.80 4031 1.23 14.27 8.42
    GK3479-024 58.00 11.40 2.50 60.71 3814 1.25 19.46 11.48
    GK3479-022 47.79 2.67 2.50 44.87 2217 1.30 12.55 7.41
    GK3479-021 45.06 5.40 2.50 47.76 2298 1.27 17.73 10.46
    GK3479-020 42.38 8.08 2.50 46.11 2296 1.28 21.53 12.70
    a by GPC with polystyrene standards
    b by H1 NMR
    • Comparative Example 3 Synthesis of random copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA) by free radical polymerization GK3365-133
  • In a 5-necked 200 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, 50.00 g of sec-Butanol (Mw 74.12 g/mol) is purged with N2 for 30 minutes and heated to 100°C. A pre-mixed feed of A 5.00 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol), B 88.54 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and C 6.46 g of tert-butyl Peroxy-2-ethylhexanoate (tBpOEH, Mw 216.32 g/mol) is fed to the reactor over 3 hours. After the completion of the feed, the reaction continues to react for a further 3 hours. The solvent is distilled off at 100oC and 10 mbar. The polymer is characterized by GPC (THF and with PS-Standards) and 1H-NMR (in CDCl3).
    Product B (g of nBA) A (g of TFOA) C (g of tBpOEH) Mn a (g/mol) PDI a wt.% TFOA b wt% F in polymer b
    GK3365-133 88.54 5.00 6.46 2065 1.56 5.35 2.95
    GK3365-134 83.54 10.00 6.46 2072 1.56 10.69 5.90
    GK3365-135 78.54 15.00 6.46 2043 1.50 16.04 8.85
    GK3365-136 88.54 5.00 3.00 2604 1.70 5.35 2.95
    • Inventive Example 4 Synthesis of a linear B-A-B Block-copolymer of n-Butyl Acrylate (nBA, A-block) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, B-block) Synthesis of A (interior) block
  • Figure imgb0008
  • In a 5000 mL glass reactor with overhead mechanical stirrer, condenser, metering pumps, computerized temperature control and data acquisition, the following A-blocks-precursors are synthesized.
    • GK3023-389 (75 units)
  • 2165.22 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 80.00 g of the initiator compound NOR 2 (342.48 g/mol) are mixed together, purged with N2 and reacted for 1.5 h at 115°C. A feed of 1624.54 g of nBA was fed to the reactor over 5 hours. At 125°C, the reaction continues for a further 2 h. Residual monomer is distilled off at 105°C and 20 mbar.
    Yield: 50.29%; GPC (THF, PS-Standard, Mn = 10740 g/mol, PDI = 1.19, viscous liquid)
    • GK3023-287 (15 units)
  • 2944.4 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 180 g of NOR 2 (342.48 g/mol) are mixed together, purged with N2 and reacted for 3.5 h at 115°C. Residual monomer is distilled off at 105°C and 20 mbar.
    Yield: 28.84%; GPC (THF, PS-Standard, Mn = 2172 g/mol, PDI = 1.25, viscous liquid)
    • GK3023-010 (35 units)
  • In a 2000 mL glass reactor with overhead mechanical anchor stirrer, condenser and metering pumps 561.36 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 50.00 g of NOR 2 (342.48 g/mol) are mixed together, purged with N2 and reacted for 2 h at 115°C. A feed of 748.48 g of nBA is fed to the reactor over 6 hours. At 120°C, the reaction continues for a further 6 h. Residual monomer is distilled off at 105°C and 20 mbar.
  • Yield: 49.67%; GPC (THF, PS-Standard, Mn = 7739 g/mol, PDI = 1.14, viscous liquid)
    • Coupling to synthesize difunctional A-blocks
  • Figure imgb0009
  • In a 5-necked 200 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, F g of Poly-nBA precursors (see table) and G g of tolylene-2,4-diisocyanate (TDI, Mw 174.16 g/mol) are mixed together and purged with N2 for 30 minutes. The inner temperature is raised to 60°C and a few drops of dibutyltin dilaurate (DBTL, Mw 631.56, 10% solution in butyl acetate) are added. The coupling reaction continues for 4 hours at 60°C. The polymer is characterized by GPC (THF and with PS-Standards and 1H-NMR (in CDCl3).
    Product A-block Poly-nBA F (g of A block) G (g TDI) Mn a (g/mol) PDI a Description (units of nBA: units of TFOA) b
    GK3041-283 GK3023-389 1200 11.00 17592 1.21 NOR-BA(150)-NOR
    GK3479-061 GK3023-010 120 2.39 8947 1.17 NOR-BA(70)-NOR
    GK3479-062 GK3023-287 100 4.79 4186 1.13 NOR-BA(30)-NOR
    • Synthesis of B block
  • Figure imgb0010
  • In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, H g of di-functional poly nBA (see table) and I g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 8 hours at 128°C. Residual monomer is distilled off at 105°C and 20 mbar. The polymer is characterized by GPC (THF and with PS-Standards; note: the refractive index of TFOA is negative) and 1H-NMR (in CDCl3).
    Product A-block Poly-nBA H (g of A block ) I (g TFOA ) Yield (%) Mn a (g/mol ) PDI a wt. % TFOA b wt% F in polymer b Idealized Description (TFOA:nBA: TFOA) b
    3479-072 GK3041 -283 40.00 5.02 95.0 2 14434 1.4 0 6.49 3.83 2.93:150:2.93
    3479-073 GK3041 -283 40.00 8.36 91.9 2 16021 1.4 0 10.02 5.91 4.89: 150:4.89
    3479-074 GK3041 -283 40.00 1.67 99.5 3 16734 1.2 4 3.55 2.10 0.98: 150:0.98
    3479-075° GK3041 -283 30.00 7.52 83.8 7 15757 1.3 6 4.67 2.75 5.86: 150:5.86
    3479-067 GK3479 -061 30.00 7.53 81.2 3 8445 1.4 5 1.59 0.94 2.79:70:2.79
    3479-068d GK3479 -061 30.00 15.06 83.8 4 9071 1.4 7 20.59 12.15 5.59:70:5.59
    3479-065 GK3479 -062 15.00 8.36 94.0 4 4749 1.3 9 31.72 18.71 2.79:30:2.79
    3479-066 GK3479 -062 20.00 3.72 94.7 0 3815 1.4 4 10.96 6.47 0.93:30:0.93
    a by GPC with polystyrene standards
    b based on solids content
    c Polymerized with a maximum temperature of 115°C in 1 hour.
    d Polymerized with a maximum temperature of 115°C in 22 hours.
    • Inventive Example 5 Synthesis of a linear A-B Block-copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NNFHA) Synthesis of A block
  • Figure imgb0011
  • The same A-blocks as those described in Example 1 are used as the starting block for the chain extension with NFHA monomer.
    • Synthesis of B block
  • Figure imgb0012
  • In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, A g of Poly-nBA (see table) and B g of 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA, Mw 318.13 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 8 hours at 128°C. Residual monomer is distilled off at 105°C and 20 mbar. The polymer is characterized by GPC (THF and with PS-Standards; note: the refractive index of NFHA is negative) and 1H-NMR (in CDCl3).
    Product A-block Poly-nBA A (g of A block) B (g NFHA) Yield (%) Mn a (g/mol) PDI a wt. % NFHA b wt% F in polymer b Description (units of nBA: units of NFHA) b
    GK3479-143 GK3023-360 10.00 10.60 92.25 2803 1.22 29.78 45.78 10:4.24
    GK3479-144 GK3023-360 15.00 9.54 91.54 2496 1.21 19.29 32.24 10:2.39
    GK3479-186 GK3023-360 20.00 7.85 89.70 2281 1.24 13.12 23.12 10:1.51
    GK3479-185 GK3023-360 20.00 4.24 88.60 2057 1.25 6.10 11.46 10:0.65
    GK3479-183 GK3023-264 30.00 14.00 91.55 3664 1.25 14.20 26.79 20:3.31
    GK3479-184 GK3023-264 30.00 9.54 92.36 3386 1.26 11.74 22.72 20:2.66
    GK3479-181 GK3023-335 30.00 8.75 93.49 5620 1.18 6.49 13.87 35:2.43
    GK3479-182 GK3023-335 30.00 5.96 93.06 5405 1.18 3.37 7.48 35:1.22
    GK3479-145 GK3023-387 35.00 11.13 94.43 11084 1.28 8.55 18.35 75:7.01
    GK3479-179 GK3023-387 50.00 11.82 95.24 11016 1.3 7.09 15.50 75:5.72
    GK3494-50 GK3023-387 50.00 7.95 96.20 98040 1.29 9.07 4.81 75:3.11
    GK3479-180 GK3023-387 50.00 7.03 95.43 2803 1.22 3.80 8.67 75:2.96
    a by GPC with polystyrene standards
    b by H1 NMR
    • Comparative Example 6 Synthesis of a linear, low polydispersity, random copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA) GK3479-202
  • Figure imgb0013
  • In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, C 50.86 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol), D 9.70 g of 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA, Mw 318.13 g/mol) and E 3.00 g of NOR 1 (317.48 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 3-4 hours at 125°C. Residual monomer is distilled off at 95°C and 10 mbar. The polymer is characterized by GPC (THF and with PS-Standards) and 1H-NMR (in CDCl3).
    Product C (g of nBA) D (g of NFHA) E (g NOR1) Yield (%) Mn a (g/mol) PDI a wt.% NFHA b wt% F in polymer b
    GK3479-202 50.86 9.70 3.00 50.79 2786 1.25 21.01 11.14
    GK3479-203 54.07 6.48 3.00 51.94 2896 1.19 17.39 9.22
    GK3479-204 57.35 3.20 3.00 49.08 2847 1.23 12.36 6.55
    GK3479-205 50.86 9.70 0.95 49.75 8146 1.18 19.62 10.40
    GK3479-206 54.07 6.48 0.95 51.24 8189 1.19 18.96 10.05
    GK3479-207 57.35 3.20 0.95 52.87 8552 1.21 5.36 2.84
    a by GPC with polystyrene standards
    b by H1 NMR
    • Comparative Example 7 Synthesis of random copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA) by free radical polymerization GK3365-207
  • In a 5-necked 200 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, 50.00 g of sec-Butanol (Mw 74.12 g/mol) is purged with N2 for 30 minutes and heated to 100°C. A pre-mixed feed of A 5.00 g of 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA, Mw 318.13 g/mol), B 88.54 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 6.46 g of tert-butyl Peroxy-2-ethylhexanoate (tBpOEH, Mw 216.32 g/mol) is fed to the reactor over 3 hours. After the completion of the feed, the reaction continues to react for a further 3 hours. The solvent is distilled off at 100°C and 10 mbar. The polymer is characterized by GPC (THF and with PS-Standards) and 1H-NMR (in CDCl3).
    Product B (g of nBA) A (g of NFHA) Yield (%) Mn a (g/mol) PDI a wt.% NFHA b wt% F in polymer b
    GK3365-207 88.54 5.00 6.46 1656 1.59 5.35 2.84
    GK3365-208 83.54 10.00 6.46 1666 1.60 10.69 5.67
    GK3365-209 78.54 15.00 6.46 1699 1.61 16.04 8.50
    GK3365-210 73.54 20.00 6.46 1606 1.65 21.38 11.33
    GK3365-211 88.54 5.00 2.00 2501 2.16 5.35 2.84
    GK3365-212 83.54 10.00 2.00 2318 1.92 10.69 5.67
    • Inventive Example 8 Synthesis of a linear A-B Block-copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluor-1-octene (TFO) Synthesis of A block
  • Figure imgb0014
  • The same A-blocks as those described in Example 1 are used as the starting block for the chain extension with TFO monomer.
    • Synthesis of B block
  • Figure imgb0015
  • In a 5-necked 200 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, A g of Poly-nBA (see table), B g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluor-1-octene (TFO, Mw 346.09 g/mol) and C g of toluene are mixed together, purged with N2 for 30 minutes and polymerized for 6 hours at reflux (106-110°C). Residual monomer and solvent is distilled off at 120°C and 20 mbar to >99%. The polymer is characterized by a mass balance of the distillate.
    Product A-block Poly-nBA A (g of A block) B (g TFO) C (g Toluene) wt.%TFO wt% F in polymer
    GM0800-0012 GK3023-360 30.00 69.22 30.00 17.81 12.64
    GM0800-0013 GK3023-360 25.00 115.36 25.00 17.81 12.64
    • III. Application Examples Static surface tension:
  • Static surface tension is measured using an OCA 20 (Dataphysics) at concentrations from 1 - 10 w% in xylene using the hanging-drop method. Table 1.1 Static surface tension
    w% TFOA surface tension (mN/m) surface tension (mN/m)
    Example type conc (w%) 10 1
    comparative Xylol (blank) 28,62 28,62
    GK3479/022 12,6 28,45 28,98
    GK3479/021 17,7 27,83 29,03
    GK3479/020 21,5 27,1 28,93
    inventive GK3479/047 3,7 28,22 28,98
    GK3479/042 10,2 20,76 25,93
    GK3494/026 14,9 18,55 21,29
    GK3494/027 24,9 18,34 19,62
  • At comparable amounts of TFOA w% (GK3479/022 as a comparative example and GK3479-042 as an inventive example), a much lower static surface tension in xylene are clearly observed (28.98 mN/m and 25.93 mN/m respectively at 1 w% in xylene).
    • Dynamic surface tension: (i) With block B containing fluorinated (meth)acrylic ester derived units
  • Dynamic surface tension is measured using a bubble pressure tensiometer (Sita) at concentrations of 0.25 % 0,5 w% in the A component of a solventbased 2K-PU. Bubble life times are measured from 80 msec up to 10 sec.
  • A component 2K PU: Table 2.1 2K-PU Component A
    Raw material Identity Weight in g. 0.25wt% Additive 0.5wt% Additive
    Macrynal SM510/60LG Acrylic resin solution 89.0
    Butyl acetate Solvent 11,0
    Efka® 2018N 8.0
    Formulation 108.0 7,38 7,36
    Additive 0.025 0.05
    Sample size 7.405 7.41
  • Efka 2018N is a commercially available defoamer.
  • At a very short bubble life time, a clear advantage (lower dynamic surface tension values) could be observed looking at same w% F-Monomer and 0.5 w% addition levels.
    Inventive examples GK3479/047 GK3479/042 GK3494/026 GK3494/027
    DST at 80 ms, 0,5 w% addition level 73,1 63,3 56,2 55,2
    w% TFOA 3,7 10,2 14,9 24,9
    Comparative examples GK3479/022 GK3479/021 GK3479/020 Efka 3600 GK3365/135
    DST at 80 ms, 0,5 w% addition level 74,7 70,8 64,9 72,8 65,1
    w% TFOA 12,6 17,7 21,5 14,2 16
    • (ii) With block B containing fluorinated alpha-olefin derived units
  • Dynamic surface tension is measured using a bubble pressure tensiometer (Sita) at concentrations of 0.1 % 1.0 w% in the A component of a solventbased 2K-PU. Bubble life times are measured from 80 msec up to 10 sec. In the following test series the commercial leveling additive EFKA 3600N is used a reference.
  • A component 2K PU: Table 2.1 2K-PU Component A
    Raw material Identity Weight in g. 0.25wt% Additive
    Macrynal SM510/60LG Acrylic resin solution 89.0
    Butyl acetate Solvent 11,0
    Formulation 100.0 19,95
    Additive 0.05
    Sample size 20,00
  • At a very short bubble life time, a clear advantage (lower dynamic surface tension values) could be observed compared to the commercial benchmark at 0.25 w% addition levels.
    Inventive examples GM800-012 GM800-013
    DST at 80 ms, 0,25 w% addition level 72.4 70.9
    Comparative examples Efka 3600N
    DST at 80 ms, 0,25 w% addition level 80.3
    • The results are also shown in Figure 1. Anticratering test:
  • The formulation, according to table 3.1, is treated for about one hour on the roll bench and finally shaken by hand until homogenous. The amount of component A indicated in table 3.2 is added in 20 ml glass jar with the appropriate amount of component B. The sample is immediately shaken by hand until homogenous and applied on a PET foil. A draw down of the mixture with 75µm wire bar at speed 20 mm/ sec is prepared. The sample is checked for craters and haze on the panels after drying over night. Table 3.1 2K-PU Component A
    Raw material Identity Weight in g. 0.1 wt% Additive 0.25 wt% Additive 0.5 wt% Additive 0.75 wt% Additive 1 wt% Additive
    Macrynal SM510/60LG Acrylic resin solution 89.0
    Butyl acetate Solvent 10.5
    Tinstab BL 2771 % in Butyl acetate Di-n-Butyltin dilaurate 0.5
    Efka® 2018N 8.0
    Formulation 108.0 7.39 7,38 7,36 7,35 7,33
    Additive 0.01 0.025 0.05 0.075 0.1
    Sample size 7.40 7.405 7.41 7.425 7.43
    Table 3.2 2K-PU Component B
    Raw material Identity blank 0.1 Additive 0.25 wt% Additive 0.5 wt% Additive 0.75 wt% Additive 1 wt% Additive
    Desmodur N75 Hardener (Resin) 2.60 2.60 2.59 2.59 2.57 2.57
    Component A 7.40 7.40 7.405 7.41 7.425 7.43
    Sample size 10 10 10 10 10 10
  • Mixing ratio: A: B=100:35 (36 round) Table 3.3 Anticrater performance in 2K-PU
    Examp. Type Sample wt% TFOA 0.1 wt% 0.25 wt% 0.5 wt% 1.0 wt%
    Craters Gloss 20° Crat. Gloss 20° Crat. Gloss 20° Crat. Gloss 20°
    comparative Blanka 8 158
    GK3479/ 020 21.5 1 165 1 93,7 1 164 1 80,2
    GK3479/ 021 17.7 4 165 1 162 1 125 1 118
    GK3479/ 022 12.6 8 165 8 98,1 8 125 2 109
    inventive GK3494/ 027 24.9 n/a 150 2 105 3 122 3 143
    GK3494/ 026 14.9 2 163 3 136 3 92 3 150
    GK3479/ 042 10.2 3 148 2 127 1 155 1 93,7
    GK3479/ 047 3.7 8 163 4 163 2 128 2 148
    comparative GK3365/ 135 16.1 2 158 7 138 7 157 4 123
    GK3365/ 134 10.7 8 164 5 158 3 152 1 162
    GK3365/ 133 5.3 8 163 6 130 3 163 2 159
    a Blank contains no additive.
    1 indicates no craters and 8 indicates many craters.

Claims (13)

  1. Use of a block copolymer which comprises at least a block A and a block B, wherein
    - the block A comprises monomer units derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, a vinyl aromatic compound, or any mixture thereof,
    - the block B comprises monomer units derived from a compound selected from
    a fluorinated (meth)acrylic ester having the following formula (I):

            H2C=CR1(C(O)ORF-1)     (I)

    wherein
    R1 is H or methyl; and
    RF-1 is an organic residue containing a perfluorinated
    C4-6 alkyl group,
    a fluorinated alpha-olefin having the following formula (II):

            H2C=CH(RF-2)     (II)

    wherein RF-2 is an organic residue containing a
    perfluorinated C4-6 alkyl group,
    or any mixture thereof,
    as a dynamic surface tension reducing additive in a coating composition, ink composition or adhesive composition.
  2. The use according to claim 1, wherein RF-1 and RF-2, which can be the same or different, have the following formula (III):

            -(R2)x-(CF2)3-5-CF3     (III)

    wherein x is 0 or 1; and R2 is a divalent non-fluorinated C1-4 alkylene group.
  3. The use according to claim 1 or 2, wherein the block B of the block copolymer has an average number of monomer units which are derived from the fluorinated (meth)acrylic ester compound of formula (I) and/or from the fluorinated alpha-olefin of formula (II) of at least 0.25.
  4. The use according to one of the preceding claims, wherein the block A of the block copolymer has an average number of monomer units which are derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, or a vinyl aromatic compound, of at least 5.
  5. The use according to one of the preceding claims, wherein the block copolymer has a number average molecular weight Mn of from 1000 to 100,000 g/mol; and/or wherein the block copolymer has a polydispersity index PDI of less than 1.90.
  6. The use according to one of the preceding claims, wherein the block copolymer comprises the monomer units derived from the fluorinated (meth)acrylic ester of formula (I) and/or from the fluorinated alpha-olefin of formula (II) in an amount of from 0.1 wt% to 70 wt%; and/or wherein the block copolymer has a fluorine content of from 0.05 wt% to 35 wt%.
  7. The use according to one of the preceding claims, wherein the block copolymer is obtained by a controlled free radical polymerization, which is preferably selected from nitroxide-mediated controlled polymerization (NMP), atom transfer radical polymerization (ATRP), or reversible addition-fragmentation chain transfer polymerization (RAFT.
  8. The use according to one of the preceding claims, wherein two neighbouring blocks are directly linked to each other.
  9. The use according to one of the preceding claims, wherein two neighbouring blocks are linked to each other via a linking group LG, the linking group LG preferably having the following formula (VII):

            -IN1'-Y'-IN2'-     (VII)

    wherein the IN1' and IN2' groups, which can be the same or different, are derived from initiator fragments IN1 and IN2 of the controlled free radical polymerization, and Y' is a divalent group covalently linked to the IN1' and IN2' groups or represents a covalent bond between the IN1' and IN2' groups.
  10. The use according to one of the preceding claims, wherein the amount of the block copolymer, relative to the total composition, is from 0.05 wt% to 15 wt%.
  11. The use according to one of the preceding claims, wherein the block copolymer is a gradient block copolymer.
  12. The use according to one of the preceding claims, wherein the block copolymer is obtained by nitroxide-mediated controlled radical polymerization (NMP).
  13. The use according to one of the preceding claims, wherein the block copolymer is obtained by nitroxide-mediated controlled polymerization using a polymerization regulator compound which is selected from one of the following formulas (IV), (V) and (VI) or based on the corresponding stable free nitroxyl radicals in conjunction with a radical source:
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
     wherein
    - R is hydrogen, C1-18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
    - R101 is C1-12alkyl, C5-7cycloalkyl, C7-8aralkyl, C2-18alkanoyl, C3-5alkenoyl or benzoyl;
    - R102 is C1-18alkyl, C5-7cycloalkyl, C2-8alkenyl, which can be unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(OH)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl;
    - G6 is hydrogen,
    - G5 is hydrogen or C1-4alkyl,
    - G1 and G3 are methyl,
    - G2 and G4 are ethyl or propyl, or G1 and G2 are methyl and G3 and G4 are ethyl or propyl; and
    - X is selected from -CH2-phenyl, CH3CH-phenyl, (CH3)2C-phenyl, (C5-6cycloalkyl)2CCN, (CH3)2CCN,
    Figure imgb0019
    - CH2CH=CH2, CH3CH-CH=CH2, (C1-4alkyl)CR20-C(O)-phenyl, (C1-4)alkyl-CR20-C(O)-(C1-4)alkoxy, (C1-4)alkyl-CR20-C(O)-(C1-4)alkyl, (C1-4)alkyl-CR20-C(O)-N-di(C1-4)alkyl, (C1-4)alkyl-CR20-C(O)-NH(C1-4)alkyl, (C1-4)alkyl-CR20-C(O)-NH2, wherein R20 is hydrogen or (C1-4)alkyl.
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CN104125984B (en) 2017-06-20
US9587105B2 (en) 2017-03-07
WO2013124421A9 (en) 2013-12-19
EP2817370A1 (en) 2014-12-31
JP2015513579A (en) 2015-05-14
CN104125984A (en) 2014-10-29
US20170009096A1 (en) 2017-01-12
WO2013124421A1 (en) 2013-08-29
US9944786B2 (en) 2018-04-17
CN104125984B9 (en) 2017-09-22
EP3778768A1 (en) 2021-02-17
US20150018476A1 (en) 2015-01-15
JP6242822B2 (en) 2017-12-06

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